Di-omega-alkynyl aryl(arylalkyl) phosphonates

ABSTRACT

INSECTIDICAL ESTERS OF CHRYSANTHEMUMIC ACID, E.G. PYRETHRINS, ALLETHRIN, ETC., FORM SYNERGISTIC INSECTICIDAL COMPOSITIONS IN COMBINATION WITH PHOSPHONATES HAVING THE FORMULA:   ((Y)M-PHENYL)-(CH(-R))N-P(=X)(-O-R1-C*CH)-O-R2-C*CH   WHEREIN R1 AND R2 ARE LOWER ALKYLENE GROUPS; R IS HYDROGEN, HALOGEN, A LOWER ALKYL OR ALKOXY GROUP, OR A SUBSTITUTED OR UNSUBSTITUTED PHENYL; N IS AN INTEGER FROM 0 TO 3, X IS OXYGEN OR SULFUR; AND Y REPRESENTS A VARIETY OF SUBSTITUENTS. THE PREPARATION AND PROPERTIES OF REPRESENTATIVE MEMBERS OF THIS NEW CLASS OF SYNERGISTIC PHOSPHONATES ARE DESCRIBED, AND TEST RESULTS OF THEIR SYNERGISTIC COMBINATIONS WITH REPRESENTATIVE CHRYSANTHEMUMATES ARE REPORTED.

v 3,555,123 ADI-MB A-ALKYNYL ARYL'(ARYLALKYL) i 'PHOSPHONATES U 1 MiltonH...Fischer, .,4032.Perry Ave. N, Robbinsdale,

Minn. 55422;: Harry Incho, 137 Ensign Ave., Medina, -N.Yl410fand*Panl,E. Drummond, 54 S. Vernon St;, andlRonaldElMontg'omery, 46S. Vernon St., bothjof Middleport, NY. 4105 No Drawing.Continuation-impart of application Ser. No. 540,175,:Apr. 5, 1966. Thisapplication June 23, 1966, Set.No.-559,745

Int. Cl. A0111 9,136,110 9/38 Claims ns'e'cticida ester of-chrys'anthemumic acid, e.g. pyrethrins,;' alle'thrin,jeto formsynergistic insecticidal com- *co'm "nationwithiphosphonates having theTh1 pp cation is a con iniiation-in-part of -co-pending appl cations" 54filed April 5, 1966, now abandonedl '"Thisinven on 'elates o novcl'insecticidal composition's 'and.ifipaiticularto insecticidalcompositions containingpyrethrins allethrin, or related insecticidalcyclopiopanecarboX-ylic acid esters, in' 'combination with certainriovel' 'syriefgists for insecticidal "activity.

Among the most widely used insecticides today are the pyrethrins, theactiye principle ofpyrethrum flowers (Chrysanthemum cinerariaefolium),which have a high .ordeflof; insecticidal activify'and a'low mammaliantoxicityn 'Ihe relatively high cost and the uncertain supply of pyrethrins..havelencoufaged attempts to prepare synthetic insecticideswhich retain the desirable properties of pyrethrins. has longlbeen knownthat synthetic products havinga basic structural similarity topyrethrins in that they are "esters of2,2-dimethyl-3-(Z-methylpropenyl)- cyclopropanecarboxylioacid (which isalso known as v chrysanthernumic acid and will be so referredto herein)exhibit insecticidal activity of a significant order. However, thesetheticchrysanthemumates are expensive "and for the iii ost part theirdegree of insecticidal activity is lower thafilthat oflpyrethrins.

The wide market ,{which pyrethrins and related synthetic insecticidesenjoy todayis-due primarily'to the discovery olf certain addit'iveswhichenhance the activity of these insecticidesf'fficse ag iditivegcommonlycalled synergists, arezagentsiwvhichzmayor inay not themselves exhibit-in-" 'sectici'dal activity-r but iwhichv-when combined with:pyrethninsziomr'elatedtrcorhpounds produce' new insecticides;having-rangeffectiveness significantly greater than the sum ofsitheeffectiveness-of :thercomponents when.v used separatelyfiA igreattdealrofatime. and. effort has been devoted toithms'earchnforgeffectivesynergists. Oneof the most'ef-v fective and mostwidelyiiusedzoi'itlie ,pyretlgfins synergists United States adan- 12,.427

is the compound piperonyl butoxide, which is described in synergisticcombination with pyrethrins in Wachs US. Patent 2,550,737.Unfortunately, ithas been found that many compoundswhich are excellentsynergists for pyrethr'ins are not nearly as efiective when used withallethrin or other synthetic cyclopr olgbanecarboxylic acid esters. a

We have now discovered that chemical compounds of the class of certainaryland aralkylphosphonate w-alkynyl esters are eifective synergists forthe insecticidal activity of esters of cyclopropanecarboxylic acids suchas the chrysanthemumates. These synergistic phosphonates have thestructural formula:

O-Rz-CECH wherein R and R are each alkylene groups of one to about sixcarbon atoms, straight or branched chain, and may be the same ordifi'erent; R is hydrogen, halogen, phenyl, substituted phenyl, a loweralkyl or a lower alkoxy group; n is an integer from 0 to 3 inclusive; Ymay be hydrogen or may represent one or more substituents includingmethylenedioxy, lower alkyl, lower alkoxy, lower alkylthio, nitro,halogen, cyano, acyloxy, acylamino, di- (lower alkyl)amino, acyl, andalkoxycarbonyl; m is an integer from 0 to 5 inclusive; and X is oxygenor sulfur. The phenylnucleus illustrated is representative of other arylgroups efiective herein, including naphthyl and pyridyl groups.

Among preferred compounds of this class are the phenylandbenzylphosphonates of the following structure:

wherein R is hydrogen or methyl; n is 0 or 1; the phenyl nucleus iseither unsubstituted or chloro-substituted; and m is 0, 1, or 2. Thew-butynyl groups may be straightor branched-chain.

Of the natural and synthetic esters of cyclopropanecarboxylic acids thebest known members, preferred for use herein because of their generalinsecticidal activity and availability, are the esters ofchrysanthemumic acid, whic have the general structure:

and wherein the radical R can be any of the very large number ofradicals which have been found to form ins'ecticidal chrysanthemumates.For example, this class of esters includes the pyrethrins, allethrin(3-allyl-2-methy1- 4-oxo-2-cyclopenteny1chrysanthernumate) and relatedinsecticides as described by Schechter and LaForge in US. Patent2,661,374; cyclethrin (3-(2 cyclopentenyl)-2-methyl-4-oxo-cyclopentenylchrysanthemumate) as described by Guest. and Stansbury in US. Patent2,891,888; furethrin (3 furfuryl-Z-methyl-4-oxo-2-cyclopentenylchrysanthemumate) 'as' described in National Distillers Products BritishPatent 678,309; barthrin (6-chloropiperonyl chrysanthemumate) and itsbromo analog, as described by Barthel et al. inzU.S. Patent 2,886,485;dimethrin (2,4-dirnethylbenzyl chrysanthemumate) and the 3,-4-dimethylisomer, as described by Barthel in'U.S. Patent 2;857,309;- com pounds ofthe classes of (cyclohexene-1,2 dicarboximido) methyl chrysanthemumatesas described-in Belgian Patent '1 646,392and'cyclohexadiene-l,2-dicarboximido chrysanthe' the'Sumitomo ChemicalCompany; Ltd. and related compounds such as phthalimidoalkyl andsubstituted phthalirnidoalkyl chrysanthemumates, as described inSumitomo Belgian Patent 635,902. Other insecticidal esters ofchrysanthemumic acid also form synergistic combinations'with thephosphonates of this invention.

The preparation ofthew-alkynyl aryland aralkylphosphonates describedherein and their synergistic insecticidal properties are illustrated inthe following ex amples, which are not intended to be lirnitative of thewide variety of procedures which are applicable to the synthesis ofw-alkynyl phosphona-tes, or of the many insecticidal combinations inwhich they are effective. In these examples, all temperatures are indegrees centigrade.

EXAMPLE 1 Preparation of di 2 propynyl [4,5 (methylenedioxy)- 2propylbenzyl1phosphonate 4,5 methylenedioxy-Z-propylbenzyl iodide wasprepared as follows: A solution of 34.2 g. of4,5-methylenedioxy-Z-propylbenzyl chloride and 30.7 g. of sodium iodidein 65 ml. of acetone was stirred under reflux for 30 utes. Theprecipitated sodium chloride was removed by filtration. The filtrate wasconcentrated and the concentrate dissolved in ether, the ether solutionWas shaken With a few drops of mercury, treated with activated charcoal,and then concentrated. The resulting brown solid was recrystallized fromhexane to give 14.9 g. of 4,5-methylenedioxy-2-propylbenzyl iodide, M.P.59-60.

4,5 methylenedioxy-Z-propylbenzylphosphonic dichloride was prepared fromthe above material as follows: A mixture of 9.4 g. of ethylphosphorodichlorite and 15.0 g. of 4,S-methylenedioxy-Z-propylbenzyliodide was heated until the quantitative amount of ethyl iodide wasdistilled. An ether solution of the reaction mixture was stirred withelemental mercury to remove iodine, then decanted [from the mercury andfiltered. The filtrate was distilled to yield 6.4 g. of4,5-methylenedioxy-2-propylbenzyl phosphonic dichloride, B.P.149-150/ca. 0.25 micron, which solidified on standing.

This material was esterified as follows: A solution of 9.7 g. ofpropargyl alcohol and 17.5 g. of triethylamine in 100 ml. of diethylether was placed in a flask, chilled, and purged with nitrogen. Asolution of 20 g. of 4,5-methylenedioxy-2-propylbenzylphosphonicdichloride in 50 ml. dry ether was added slowly during 30 minutes. Whenaddition was complete, the mixture was allowed to warm slowly to roomtemperature. Stirring was continued for 4 hours. The mixture wasfiltered, and the filtrate was distilled under reduced pressure to givedi-2-propynyl[4,5-(methylenedioxy)-2-propylbenzyl]phosphonate which, onredistillation, distilled at 171-5 0.1 micron.

Analysis.-Calcd for C H PO (percent): C, 61.08; H, 5.73; P, 9.27. Found(percent): C, 61.01; H, 5.69; P, 9.13.

EXAMPLE 2 The synergistic activity ofdi-2-propynyl[4,5-(methylenedioxy)-2-propylbenzyl]phosphonate Thesynergistic activity ofdi-2-propynyl[4,5-(methylenedioxy)-2-propylbenzyl]phosphonate withallethrinwas determined by the following test procedure: The testcompound-and allethriu were dissolved in a solvent of 70 parts by volumeof acetone, which was then made up to 100 parts by addition of water. Agroup of thirty to forty housefiies (Musca domestica L.), immobilizedunder carbon dioxide, was placed on a moist filter paper held on aBuchner funnel attached to a vacuum source. Twenty-five ml. of the testsolution was poured over the immobilized fiies, thisbeing sufilcientvolumethat all were completely immersed. Vacuum wasithen applied toremove the test;so lution', and the flies weretransferred to holdingcages lined with absorbent paper. Mortalitycounts were made; after 24hours; Results are shownin Table 1,. for varying ratios;

and concentrations of synergist and allethrin. In this and subsequenttables, "the amounts of the" test ingredients are stated inconcentration terms of mg. per 100 ml. of test solution.

TABLE}. [COMPOSITIONS 0E DI-2-PROPYNYL' [4,5.- METHYLENE- m oigga-PnopyLBnNzrLgyrroslgfaoNATE AND ALL- Synergist, 2 milligramsEXAMPLES (p y I Preparation of di-3-butynyl phenylphosphonate A mixtureof 15.1 g. 3-butynlol and 21.9 triethylamine in '100 mlfdithyletli'er'wasfilaed in a ilask and chilled in an ice bath whileihesystern,wasgpurged with dry nitrogen. A solution of ,200 g. of..phenylphosphorric dichloride in ml. of dry ether wagslowly addedguring30 minutes. The mixture was then allowed to comet0 room temperature,while stirring was continued for four hours. The mixture was filtered,,and the "filtrate was distilled using an oil diffusion system. A'foi'erun was collected to a pot temperature of '162 &'0.2. rnicron, andthe product was collected at a pot temperature of 162194. The crudeproduct was redistilled at a pressureless than 0.1 micron, to givedi-3-butynyl phenylphosphonate'which distilled from a pot at 162 (headtemperature 122-130 after a small forerun.

Analysis.-Calc.d for C H 0 P (percent): C, 64.12; H, 5.77; P, 11.81.Found (percent): C, 63.97; H; 5.77;.1, 11.65. EXAMPLES'-4-,8-

The synergistic activity of di-3-butynyl phenylpho's phonate with a widevariety=of chrysanthemumate esters was evaluated against housefiies bythe following procedure: About one microliter o'f ,a solution containingthe indicated amount of the test materials in ml. "of acetone wasapplied topically to eachof 35 .to 45 threeto four-day old housefiies(Musca domestica) in oneto four replicates. After twenty-four hours themfortalityyvas deter-mined by physical counting of thedeadand'. livingflies, and the percent kill was calculated- Results are shown in Table2.

TABLE 2.COMPOSITIONS 0F DI-3-BUTYNYL PHENYL- PHOSPHONATE ANDCHRYSANTHEMUMATES I "Mortality of Synergist, houseflies,Chrysanthemumate Milligrams milllgrams percent Cyclethrin 14. 4 72 30None 9 24 None 9 Allethrin m4 7'2 91 None .'160 Z" D 24 None 1 w 11Pyrethrins 14.4 2 ..72" 8 9 None I Dimethrin .14.

' None (l cyclohexene-l,2-dicarboxim- '14. 4 1do)metl1yl ehrysanthemueNone' mate. I .20

. gisticeffect'was; observedwhen combined phrysarr.

Synergistic activity was tested against the German cock roach (Blatellagermanica) as follows: Adultymale...

roaches were completely immersedQfor'about fiveseconds in test solutionsconsisting of di-3-butynyl phosphonate and the indicatedchrysanthemumate'ester, in 50% aqueous acetone. The roaches were thentransferred to holding cages, and themortality was determined aftertwentyfour hours. Five replicates of nineteen or twenty roaches eachwere run at each concentration, which is given in the table as mg.per-100 ml. solution. The results shown in Table 3 represent theaverages ofieach set of five replicates.

TABLE 8.-'COMPOSITIONS OFYDI-3-BUTYNYL PHENYL- PHOSPHONATE ANDCHRYSANTHEMUMATES Preparation of di-3-butynyl(4-chlorobenzyl)phosphonate A mixture of 12.1 g. 3.-butyn-1-ol and 17.5g. triethylamine in 100 ml. of diethyl ether was placed in a flask andchilled in an ice bath whilethe system was purged with dry nitrogen. Asolution of 20.0 g. of 4-chlorobenzylphosphonic dichloride in 50 ml. dryether was added slowly during 30 minutes. The mixture was then allowedto come to room temperature, while stirringwas continued for four hours.The mixture was filtered, and the filtrate was distilled under reducedpressure togive, after a small forerun, 12.9 g. of pale/yellow oil whichdistilled at a pot temperature of 168-190? (head temperature 139-145)"under 0.5-0.8 micron. Redistillation under pressure of less thanone micron gave colorless liquid di-S-butynyl(4-chlorobenzyl)phosphonate (pot temperature 157184; head temperature11.6-150). j

Analysis.Calcd for C H ClO P (percent): C,

eifect is observed.

6 phosphonate of this invention, and a-.var;iety of chrysans themumates.A consistent andjsubstantial synergistic H EXAMPLE 18 1 The synergisticactivity of di-3-butynyl (4 chlorobenzyl) phosphonate in combinationwith representative chrysanthemumates useful herein was determinedagainst the 'German'cockroach, following the procedure described inExample Results are given in Table 5.

TABLE 5.COMPOSITIONS OF DI-3-BUTYNYL i-CHLORO- .BENZYL)PHOSPHONATE ANDCHRYSANTHEMUMATES Mortality of Synergist, roaches, chrysanthemumateMilligrams milligrams percent Allethrin 10 100 100 None 100 0 None 10 010 None 2 (l-oyclohexene-l,2-dicarboxi- 100 100mido)methylchrysanthemumate None 100 0 10 89 None 10 0 10 None 0 EXAMPLE17 Preparation of bis(l-methyl-2-propynyl) phenylphosphonate Followingthe procedure described in Example 3, 22.8 g. of 3-butyn-2-ol wasreacted with 30.2 g. of phenylphosphonic dichloride. The final productWas distilled using an oil diifusion system, and collected over a pottemperature of 140-176 and a head temperature of 100-128 at 0.6 micron,and then redistilled at a pot .temperature of 131-138 and a headtemperature of 57.98; H, 5.19; P, 9.70. Found (percent): C, 57.78; H,

EXAMPLES 1 1-15 The synergistic activity of di-3-butynyl(4-chlorobenzyl) phosphonate with a wide variety of chrysanthemumateesters was evaluated against houseflies, employing the proceduredescribed for Examples 48. Results are given in Table 4.

TABLE 4.COMPOSITIONS OF DI-3-BU'IYNYL (4-CHLORO- BENZYL)PHOSPHONATE ANDCHRYSANTHEMUMATES The results .shown intil able ri -continue todemonstrate, the general nature of the synergistic interaction between aperature of 146-148" at 0.1 micron.

-l01 at 2 microns.

Analysis.Calcd. for C H O P (percent): C, 64.12; H, 5.77; P, 11.81.Found (percent): C, 63.92; H, 5.92; P, 11.61.

EXAMPLE 18 Preparation of di-3-butynyl 1-(phenyl)- ethylphosphonateFollowing the procedure described in Example 10, 14.9 g. of 3-butyn-l-olwas reacted with 22.7 g. of 1- (phenyl)ethylphosphonic dichloride. Thefinal product was distilled using an oil diffusion system, and collectedat a pot temperature of 177-190 and a head temperature of 121-123 at 0.4micron.

Analysis.Calcd for C H O P (percent): C, 66.20; H, 6.60; P, 10.67. Found(percent): C, 66.46; H, 6.58; P, 10.36.

-EXAMPLE 19 Preparation of di-3- butynyl 2,4- dichlorobenzylphosphonate1 ,Following the procedure described in Example 10, 5.5 g.of"3butyn-1-olwas reacted with 10.2 g. of 2,4- dichlorobenzylphosphonic' dichloride.The final product was distilled using an oil diffusion system, andcollected overa pot temperature of 206-2l0' and a head tern-Ahalysis-Calcd for C H C1 O -P (percent): C. 52.20; H, 4.38; P, 8.97.Found (percent); C, 52.28; H,

EXAMPLES 20 1:0 43

a :Following the general procedures exemplified above, a large number ofcompounds of this class are readily synthesized. ,The synergisticactivityoftypical phosphonates of this irivention, in combination withtypi al and useful chrysanthemumates, is further illustrated in Table 6.:These results were obtained described in Example 2.

following the procedure TABLE 6.-SYNERGI STIC INSEOTICIDAL COMPOSITIONSMortality I r ,i ,oi houseflies, Cln'ysanthemumate V MilligramsPhosphonate Milligrams I "percent Allethrin y 10 Di-3-butyny1 I v 50--100 None benxylpho sphonate. 50 10 None 34 (lcyelohexene-l,Z-dlearboximido) 10 Di-3-bntynyl v 50 I I y 1 00 1 methylchrysanthemumate. None (1-phenylethyl)- 50 10 phosphonete. Nonelyrethrins 10 Di-3-butynyl (2,4- n so None diehlorobenzyl) 50 10phosphonate. None Allethi'in Di-(1-methy1-2-propynyl) 50 Nonephenylphosphonate. 50 5 None Allethrin Di-3-butynyl (34 Nonedichlorobenzyl) 50 10 phosphonate. None (1 cyelohexene-l,2-diearboximido) 10 Bis (1methyl2-propynyl) 50 methyl chrysanthemumate.None (4-chlorobenzyl)- 50 10 phosphonate. None Cyclethrin 10Di-2-propynyl 50 None (4-chlorobenzyl) 50 10 phosphonate. None 12Allctln'in 10 Di-4-pentynyl 50 100 None (4-ch1orophenyl)- 50 0 10phosphonate. None 34 Pyrethrins 5 Di-2-propynyl 50 44 None(Z-methylbenzyD- 50 0 5 phosphonate. None 4 Alletlirin 5 Di-2-pro ynyl50 97 None pheny phosphonate. 50 0 5 None 6(l-oyelohexene-l,2-diearb0ximido) 10 Di-4-pentynyl 50 100 methylchrysanthemumate. None phenylphosphonate. 50 0 l 10 None 10 2 3Allethrin 5 Di-2-pro ynyl 50 92 I l None pheny phosphono- 50 0 5thioate. None 6 v Allethrin 10 Di-(1-methyl-3-butyny1) 50 97 f- Nonephenylphosphonate. 50 0 V 10 None 34 Alletlirin 10 Di-3butynyl[4,5-(methyl- 50 100 None enedioxy)-2-propyl- 50 0 10benzyl1-phosphonate. None 34 Allethrin 10 Di-3-butynyl (diphenyl- 50 100None methyD-phosphonate. 50 18 10 None 34 Pyrethrin 1o Di-3-butynyl(4-fiuoro- 50 100 None benzyl)-phosphona.te. 50 0 10 None 3 i Pyrethrin10 Di-3-butynyl (4- 50 100 None bromobenzyl)- 50 7 10 phosphonate. None3 Allethrin 10 Di-3-butyny1 (3-ch10ro- 50 100 A None benzyD-phosphonate.0

10 None 34 Allethrin 10 Bis(1-propyl-2-propynyl) 50 94 None(4-chlorobenzyl) 50 0 10 phosphonate. None 34 V Cyelethrin 10Bis(1-methyl-2-propynyl) 50 100 None (4-ehlorobenzyl)- 50 0 10phosphonate. None 12 Pyrethrin 10 Bis(1-methyl-3-butynyl) (4- 60 95 NonechlorobenzyD-phos- 50 8 10 phonate. None 3(l-cyelohexene-1,2,-dicarboximido) 10 Di-3-butynyl 50 methylchrysanthemumate. None (4-nitro-benzyl-)- 50 0 1O phosphonate. None 10Allctln'in 10 Di-3-butynyl (2- 50 100 None phenylethyl) -pl1os- 50 8 10phonate. None 34 Alletlirin 10 Di-3-butyny1 (3- 50 100 Nonepheny1propy1)-phos- 50 10 7 10 phonate. None 34 -Many.other synergisticcombinations, in addition to those specifically exemplified herein, willbe obvious .in view of the teachings hereof. The-novel synergisticcornbinations described herein are effective over a wide range 75Chemical Specialties Manufacturers Assoeia ti 1 The method usedwesthe-0fiicialMethod-efi-the evaluating liquid. household '"insecticidessagainst ,flying insec s, 11961; Rfe' ifiseapgamrcheme i i 7 239. Thi sproof 100' to 3'00 'eplicate, and test compositionspreaired astfollowsiFift'yir'ig. of (:l 'cyclohekene1,2 dicaramiaokm thyl cfirysamhe 'nvma't'a'nd the desired i a yl phenylphosphonate were added I ZQQIihl. ofa s llend; consistingof approximately 5.57 mar nara, r de and i. 95.5.%rpetroleumdistillate. Thes'e'testlcoinpos ons' wereap'plied to thechambers in Iheiamountiof {:12 mlfjof 'icomposition per 216 cubic hAfter hours the mortality was determined by physicalcounting" of thedead aridliving flies. Two to were: run, including controls containingthe omp" sm ar thisls'ynergistic combination. Re-

Table 7, are given in mg. per 100 ml. of

TABLE "7. INSECTIGTDAL ACTIVITY or VARYING RATIOS 39 i Q-QM-PON NKnockdown Mortality 1 1 10 minutes; 24 hours,

percent percent As' showndn' Table 7, -even at relatively lowproportions of (l-cyclohexerw1,2-dicarboximido)methyl chrysantheintimateand di-3-buty'nyl phenylphosphonate a marked synergisticefiect isobserved With this particular combination of' components theoptimumratio is shown to be" veraboiltfl'zil, 'aiidof course' synergisticeffectiveness aintained'afhighef ratios ofphosphonate tochrysantlifeniuhia'tefNote, hov vvegthat even 500 mg. of thephosphonat'e alane'kmed 6" y -2% 'of the test insects. It is(if-particular interest observethat this phosphonate enhances to"anffiiiiisual extehfithe percent kill of this chrysaritliemumate' whibb'y' itself exhibits good knockdowner houseflies bu very "poor permanenteffectiveness. Ina'dditiOn' tq'thefspecifie di 'w-alkynyl phenylandbenz'ylphosphonatesieireinplified herein, similar synergistic behaviorcharacteriies 'theiother members of the class described, including" butfnotlimited to the following: Bis I methyI-S -butynyl).(3-chloropheny1)phosphonate; di-S-hexynyl (.45chlorophenyl) phosphonate;3-butynyl 2-propynyl (Z-chlorophenyl)phosphorothionate; di-S-hexynyl(2,4,5-trichlorophenyl)phosphonate; di-4-pentynyl (2,3,6-trichlorobenzyl phosphonate; di-3 butynyl (2,3,4,6tetrachlorophenyl)phosphonate; di-S-butynyl(2,3,4,5,6-pentachlorophenyl)phosphonate; di-6-heptynylphenylphosphonothionate; di- 'I-octynyl benzylphosphonate; 3ab'utynyl l-methyl-2-propynyl benzylphosphonothionate; bis(2-methyl-3-butynyl)S-methylbenzyl) phosphonate; bis(Zafiethyl4apentynyl)'(4-e'thylphenyl)phosphonate; bis(4 niethyl-fi-hexynyl)(2-bromopheny1)phosphonate; bi "1 methyl+4-pehtynyl (ch1oro)'-(4chlorophenyl') I ethyl]phosphonate;-=-

:HJ butyny-b[4-(methylthio)benzynphosphonate; i '-"fdiIn"ethyl-3butynyl-)benzylphosphonate; r 1 bis( methyl-=-hexynyl)phenylphosphonate; d btitynyl'a-[i-( propylthio)phenyl]phosplionate; 1di-3-butyny1 (l-phenylpropyl)phosphonate; bis(2-ethyl-3-butynyl)(2-propylphenyl)phosphonate; di-3-butynyl(4-isopropylpheny1)phosphonate; di-Z-propynyl [4-(e thy lthio benzyl]phosphonate; di-2-propynyl (3,4-dimetho ryphenyl)phosphonate; bis(I-ethyI-Z-methyI-S-butynyl) (4-cyanobenzyl) ph sphonate;

di-3.-butynyl (4-iod0benzyl)phosphonate;

di-3 ebutynyl 2-.eth0xybenzyl) phosphonate;

di'- 3abutynyl (4-acetoxyphenyl)phosphonate;

bis( 3-ethyl-4-pentynyl) (2-chloro-4-methoxybenzyl) phosphonate;,

di-S butynyl (4-propionyloxybenzyl) phosphonate;

di-2-propynyl [2- (methoxycarbonyloxy)phenyl] phosphonate;

.di-Z-propynyl [4-(ethoxycarbonyloxy)benzyl] phosphonate;

di-S-butynyl [3 (diethylcarb amyloxy) phenyl] phosphonate;

bis (2-ethyl- 1 ,3 ,3 -trimethyl-5-hexynyl) [4- (acetylamino) phenyl]phosphonate;

di-3-butynyl [4- (dimethylamino phenyl] phosphonate;

di-3 -butyny1 [3- (diethylarnino) phenyl] pho sphonate;

di-2-propynyl 3 -acetylphenyl) phosphonate di-3-butynyl(4-pr0pionylbenzyl)phosphonate;

di-Z-propynyl [2- (methoxycanbonyl) benzyl] phosphonate;

di-3 -butynyl [4- (ethoxycarbonyl phenyl] phosphon ate;

di-3-butynyl [di-(4-ch1orophenyl)methylJphosphonate;

di-3 -butynyl [(4 chlorophenyl) (phenyl)methyl] phosphonate;

di-4-pentyny1 [di 4-methoxyphenyl) methyl] phosphonothionate;

bis 1-propyl-2-propynyl) (4-chlorophenyl) (ethoxy) methyl]-phosphonate;

di-3-butynyl [(2,4-dichlorophenyl) (methoxy) methyl] phosphonate;

di-Z-propynyl 1- 3 ,4-dichlorophenyl) pentyl] phosphonate;

di-3 -butynyl (bromo) (phenyl) methyl] phosphonate;

bis 1-ethyl-2-propynyl phenylphosphonate;

bis( 1 -ethyl-3 -buty-ny1) benzylphosphonothionate;

bis( l-methyl-2-p ropynyl) (3 ,4-dibromobenzy1) phosphonate;

ibis (,2-methyl-3 -butyny1) (3 -nitrobenzyl phosphonate;

bis( 1-methyl-3 -butynyl) (3-chlor0-4-nitrobenzyl) phosphonate;

di-S-butynyl (3-chloro-4-methylphenyl)phosphonate;

di-Z-propynyl (3-chloro-4-methylphenyl) phosphonothionate;

bis( l-methyl-1-propyl-4-pentynyl) [2-( 3,4-dichlorophenyl)-1,2-dimethylethyl] phosphonate; and

bis 1-ethyl-2-propynyl) (4-chlorobenzyl) phosphonate.

The novel synergists of this invention may be prepared by adaptation ofthe synthetic procedures illustrated above, as well as by otherprocedures. Some generally useful methods for the preparation of thesecompounds are discussed below.

These w-alkynyl esters may be prepared by reaction of the appropriatealkynol, or a salt thereof, with the desired phosphonic dihalide,normally the dichloride, in the presence of a strong organic orinorganic base. Mixed esters may be prepared by standard procedurestherefor, such as reaction with a mixture of alkynols, or successivereaction steps to prepare first the monoester and then the desireddiester. The preparation of phosphonic dichlorides is described indetail by Sasse in Houben-Weyl, Methoden der Organischen Chemie, 4thEdition, Volume 12, page 348 et seq. Useful methods for the preparationof phosphonic dichlorides include their preparation from phosphorustrichloride, by first reacting with an appropriately substitutedaromatic hydrocarbon to produce a phosphonous dichloride, which onreaction with elemental chlorine gives an arylphosphonium tetrachloride,

by reaction of an aryldiazonium tetrafluoroboride with phosphorustrichloride to form the corresponding phosphonic acid, which is readilyconverted to the phosphonic dichloride.

Another useful preparative method employs the Michaelis-Arbusovreaction, wherein an aralkyl halide, preferably the chloride or bromide,is reacted with a trialkyl phosphite to form a dialkylaralkylphosphonate, which is readily converted to the desired phosphonicdichloride. A modification of the Arbusov' reaction (Kosolapoff,Organophosphorus Compounds, John Wiley, New York, 1950, page 123)involves reaction of the arylalkyl halide with a metal salt of a dialkylphosphite to give the corresponding dialkyl arylalkylphos phonate, whichis then converted to the phosphonic dichloride.

In cases where the substituents on the aromatic ring, such as in themethylenedioxybenzyl compound, are susceptible to attack by thehalogenating agents, reaction of the appropriately substituted benzyliodide with ethyl phosphorodichloridite may be used to give thecorresponding benzylphosphonic dichloride directly.

The analogous phosphonothionates may be prepared from the correspondingphosphonothioic dichlorides and the alkynol. Preparation of the requiredphosphonothioic dichloride is accomplished from starting materialssimilar to those for the phosphonic dichlorides. Treatment of thephosphonium tetrachlorides with the hydrogen sulfide or phosphoruspentasulfide gives directly the desired phosphonothioic dichloride.Aluminum chloride complexes, obtained when phosphorus trichloride reactswith a hydrocarbon in the presence of aluminum chloride, may be reacteddirectly with free sulfur, to yield the corresponding phosphonothioicdichloride. Reaction of a preformed phosphonic dichloride withphosphorus pentasulfide replaces the oxygen with sulfur, thus providingthe corresponding phosphonothioic dichloride.

These and other procedures are readily adapted to produce arylandaralkylphosphonic dichlorides having the variety of substituents usefulherein, by appropriate choice of starting materials and reactionconditions. These phosphonic dichlorides are reacted with the desiredw-alkynol by standard procedures, including those exemplified herein andother known procedures for the preparation of walkynyl esters ofphosphonic acids.

The novel synergists described herein have a degree of eifectivenesswhich is not shared by closely related compounds. The nature andlocation of the unsaturated linkage has been found to have a markedeffect on the synergistic effectiveness of this type of compound.Displacement of the acetylenic linkage from the terminal positiondiminishes the synergistic activity.

The synergistic compositions of this invention may be employed tocontrol a variety of crop pests and household pests. They are notusually applied full strength, but are generally incorporated with theadjuvants and carriers normally employed for facilitating dispersion ofactive ingredients for insecticidal applications, recognizing theaccepted fact that the formulation and mode of application may affectthe activity of a material. Striking results are obtained when thesecompositions are applied as space sprays and aerosol sprays, forexample, or are formulated into any of the diluted and extended types offormulations used in insecticidal practice, including dusts, wettablepowders, emulsifiable concentrates, solutions, granulars, baits, and thelike, for application to foliage, within enclosed areas, to surfaces,and wherever insect control is desired.

These synergistic compositions may be made into liquid concentrates bysolution or emulsification in suitable liquids, and into solidconcentrates by admixing the active components with talc, clays, andother solid carriers used in the insecticide art. Such concentratesnormally contain about '580% of the toxic composition, and the restinert material which includes dispersing 12, agents, emulsifying agents,andiwettih g ag'ents For prac tical applicatiom'theconcentrates; arenormally diluted with water or other liquidforfliquid sprays, withliquefied propellants for aerosols," or 'with,'additional solid carrierfor application'as a dust or granular formulation. EBaits: areusuallyprep'ared by mixing such concentrateswitfia suitable insect food,such as mixtures of cornmealah'd sugar, and insect"a'ttractants may"also'be presenL The concentration'of the active ingredients in thedilutedfo'r} mulations, as generally applied rsr'fmn rbr of insects, isnormally in the range of about Q'.00l %,to' about '5'% Many variationsof sprayng and dusting compositions are well known in the art, as arethetechniques foriforniw lating and applying these compositions. I

Employing the synergisticinsecticidalcomposition de scribed herein,enhancedcontrol isgobtained'of 'bo'tli' crop and household pests,including insects'against the cyclopropane carboxylates are themselveseffectivefibut' at higher concentrations.- This includes flying andcrawl: ing pests of the orders Coleoptera' (beetles), Hemiptera (truebugs), Homoptera (aphids), Diptera (flies), ,Orthoptera (roaches),Acarina mitesjan'dfticks)'; and -Lepidoptera (butterflies and mothsincluding their larvae). Because of the low mammalian toxicity of thesecompositions, they are preferred compositions for use in control ofpests in an environmentinhabi'ted by man and animals, including controlof flies, mosquitoes, ants, roaches, moths, ticks, and the like, as wellas in uses such as: packaging, food and grain protection, and garden,pet, and livestock uses.

The relative amounts of synergist and cyclopropane; carboxylate(chrysanthemumate) employed are not critical, in that a relatively minoramount, e.g., less than one part of synergist per part ofchrysanthemumate, is ef fective in imparting a beneficial effect to thecombination. From practical considerations, it is preferred to uselarger amounts of synergist, for example, from fivefto, twenty or moreparts of synergist per part of cyclopropanecarboxylate. Even largerproportions of synergist may be employed without detriment, whether ornot the optimum synergistic proportions have been achieved. It is clearthat effective amounts of synergist should be employed in thecompositions, that thecomponents should be present in synergisticproportions, and that effective amounts of the compositions, to controlthe particular insect pests in the environment of infestation, should beapplied.

It is apparent that many modifications maybe made in the formulation andapplication of the compositions of this invention, without departingfrom the spirit and scope of our invention, and of the following claims:

We claim:

1. Compounds of the class 13 wherein R is selected from the groupconsisting of hydrogen and methyl, n is an integer of 0 to 1 inclusive,and m-is an integer of 0 to 2 inclusive.

3". The compound of claim 2 of the formula di-3-butynylphenylphosphonate.

4. The compound of claim 2 of the formula di-3-bu- 5 tynyl(4-chlorobenzyl)phosphonate.

5. The compound of claim 2 of the formula di-S-butynyl*benzylphosphonate.

6. The compound of claim 2 of the formula di-3- butynyl1-(phenyl)ethylphosphonate.

7. The compound of claim 2 of the formula di-3-butynyl2,4-dichlorobenzylphosphonate.

8. The compound of claim 2 of the formula bis(1-methyl-Z-propynyl)phenylphosphonate.

9. The compound of claim 2 of the formula di-3-butynyl3,4-dichlorobenzylphosphonate.

References Cited UNITED STATES PATENTS CHARLES B. PARKER, PrimaryExaminer 10 A. H. SUTTO, Assistant Examiner US. Cl. X.R.

